CN1599760A - Anionic copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions - Google Patents

Anionic copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions Download PDF

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CN1599760A
CN1599760A CNA028243889A CN02824388A CN1599760A CN 1599760 A CN1599760 A CN 1599760A CN A028243889 A CNA028243889 A CN A028243889A CN 02824388 A CN02824388 A CN 02824388A CN 1599760 A CN1599760 A CN 1599760A
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acid
acrylamide
water
vinyl
multipolymer
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CN1266176C (en
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理查德·李·布雷迪
威廉·肖恩·凯里
约翰·C·哈林顿
布赖恩·L·沃尔柯克
张福山
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Hercules LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/916—Interpolymer from at least three ethylenically unsaturated monoolefinic hydrocarbon monomers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polymerisation Methods In General (AREA)
  • Artificial Filaments (AREA)

Abstract

A papermaking method and a composition which utilize, as a drainage aid, a water-soluble anionic copolymer prepared via a water-in-oil polymerization technique that, absent a crosslinking agent, is characterized by a Huggins' constant (k') determined in 0.01M NaCl greater than 0.75 and a storage modulus (G') for a 1.5 wt.% actives polymer solution at 4.6 Hz greater than 175 Pa.

Description

Anionic copolymer that in the reversed-phase emulsion matrix, makes and the application in the preparation of cellulose fiber fiber products thereof
Technical field
The present invention relates to the application in preparation cellulose fiber fiber products by inverse emulsion polymerization synthetic water-soluble anionic copolymers and described multipolymer.The invention still further relates to the cellulose fiber fiber products that is mixed with water-soluble anionic copolymers, as paper and cardboard.
Background technology
The cellulosic fibre thin slice particularly preparation process of paper and cardboard comprises the steps: 1) preparation cellulosic fibre aqueous slurry; Wherein can comprise inorganic mineral additive or pigment; 2) slurry is deposited on the mobile paper making wire cloth; 3) form thin slice through the dehydration back by the solids component in the slurry.
The thin slice that said process forms is further removed moisture through extruding and drying again.For cost, the raising process velocity that reduces described papermaking process, and/or make final paper product have property, before the thin slice moulding, in slurry, add organic and inorganic additives usually.
Paper-making industry is constantly being made great efforts to improve paper quality, increase productive rate, to reduce manufacturing cost.Usually add chemical before fibre stuff arrives paper making wire cloth for this reason, improve drainage/dehydration property and solid retention, these chemical are called retention aid and/or drainage aids.
The draining of fibre stuff or dehydration normally improve the restriction step of throughput rate on the paper making wire cloth.Can in extruding and drying process, obtain more exsiccant thin slice by improving syneresis, thereby reduce steam consumption.In addition, this also is the step of the final performance of the multiple scraps of paper of decision in papermaking process.
Keep situation as for solid, in the process of turbulent flow drainage and formation paper web, need to add Retention Aid in Papermaking to increase solid fine particle keeping on silk screen.If these solid fine particles do not have enough retentions, they may be discharged in the plant effluent or accumulation and depositing in circulation plain boiled water.And insufficient retention can cause the loss that should be adsorbed on the additive of giving corresponding paper opaqueness, intensity or sizing material character on the fiber, thereby has raised the papermaking cost.
Usually use and have the high-molecular weight water-soluble polymers of plus or minus electric charge as retention aid and drainage aids.Nearest studies show that: the inorganic particles that is used in combination with the high-molecular weight water-soluble polymers as retention aid and drainage aids has excellent more keeping and drainage effect than the molecular weight water-soluble polymers of using traditionally.United States Patent (USP) 4,294,885 and 4,388,150 use starch polymer and silica gel.United States Patent (USP) 4,753,710 usefulness high-molecular weight positively charged ion flocculation agent make the pulp material flocculation, produce shearing force in the pulp material of flocculation, add wilkinite then in slurry.United States Patent (USP) 5,274,055 and 5,167,766 disclose a kind of organic fine particles that uses chemically crosslinked in paper-making process or the little polymers method as retention aid and drainage aids.
In paper manufacturing systems, also can use multipolymer to control the deposition of contaminant or organic sediments.That organic sediments is meant is viscosity, water-fast, the production of paper is had the material of destruction.Be known as pitch or wood pitch in slurrying and this foreign material of paper-making process, and goo is meant the binding agent that is sticky with thing introducing paper-making process from regenerated fibre from timber.One of method of eliminating these impurity is flocculated into big, inviscid particle to organic sediments, and these particles can be removed from paper making pulp or combine with paper and can not produce defective in paper.The chemical that can alleviate their side effect with the organic sediments reaction comprises tensio-active agent and polymkeric substance.Described polymkeric substance can be ionic or non-ionic type, comprising the material as flocculation agent, flocculation agent and dispersion agent.
The used polymkeric substance or the effect of multipolymer change with following condition: the monomer, the arranging situation of monomer in polymkeric substance, the molecular weight and the preparation method of synthetic molecules that form polymkeric substance.The present invention relates generally to this feature of back.
It should be noted that the water-soluble anionic copolymers of preparation has beyond thought unique physical character under certain conditions.And described polymkeric substance shows the activity of unanticipated in Application Areass such as comprising the retention aid of paper industry, drainage aids and contaminant conditioning agent.Although those skilled in the art is rather familiar to synthetic method of the present invention, do not mention the activity that can obtain unique physical of the present invention and unanticipated in the technology in the past.
Summary of the invention
The present invention relates to water-soluble anionic copolymers and contain the cellulose fiber fiber products cellulose sheet of paper or cardboard (particularly as) of described multipolymer.The invention still further relates to a kind of method for preparing described multipolymer and cellulose fiber fiber products.
On the other hand, the invention provides a kind of method for preparing the cellulose fiber fiber products, it comprises add water-soluble anionic copolymers (shown in the following molecular formula I) in described cellulose paste.The invention still further relates to the cellulose fiber fiber products, it comprises a kind of aqueous cellulosic paper pulp that contains described water-soluble anionic copolymers.Multipolymer is meant the unitary polymkeric substance of the different monomers that comprises two or more herein.
The inventor is surprised to find that some anionic copolymer for preparing possesses the unique physical property and the character of unanticipated under specific polymerizing condition.Anionic copolymer of the present invention is that especially one or more anionic monomers prepare by inverse emulsion polymerization by one or more water miscible monomers.The gained anionic copolymer is water miscible.
Anionic copolymer molecular formula of the present invention is as follows:
[B-co-F-] (Formula I)
Wherein B is the non-ionic polymers segment that forms after one or more non-ionic monomer polymerizations; F is the anionic polymer chain section that the unsaturated anionic monomer polymerization of one or more vinyl forms; The mol ratio of B and F was from 5: 95 to 95: 5; " co " is meant by two or more monomer components does not have particular arrangement and the polymeric system that forms.And, this preparation process is undertaken by the water-in-oil emulsion method under the cross-linking agent-free condition, the Huggins constant that described polymkeric substance records in 0.01M NaCl is greater than 0.75, and contain the described copolymer solution of 1.5 weight % activess in the storage modulus of 4.6Hz (G ') greater than 175Pa.
Detailed Description Of The Invention
The invention provides the water-soluble anionic copolymers that possesses unique physical character, described multipolymer the preparation method, comprise in cellulose paste the cellulose fiber fiber products preparation method who adds described water-soluble anionic copolymers.The universal architecture of water-soluble anionic copolymers of the present invention is shown in Formula I.
[B-co-F-] (Formula I)
Non-ionic polymers segment B is the repeating unit that forms by after one or more non-ionic monomer polymerizations in the Formula I.The monomer that comprises among the B for example but be not limited to following these: acrylamide, Methacrylamide, N-alkyl acrylamide (as N methacrylamide), N, N-dialkyl group acrylamide is (as N, the N-DMAA), methyl acrylate, methyl methacrylate, vinyl cyanide, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate, the N-vinyl pyrrolidone, alkyl acrylate, alkylmethacrylate, alkyl acrylamide, the alkyl methyl acrylamide, alkoxide acrylate and methacrylic ester are (as the alkyl polyethylene glycol acrylate, or the mixture of above-mentioned substance and analogue thereof the alkyl polyethylene glycol methacrylate-styrene polymer).
Anionic polymer chain section F in the Formula I is the repeating unit that forms by after one or more anionic monomer polymerizations.The monomer that comprises among the F for example but be not limited to following these: vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, acrylamide oxyacetic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid, the 2-acrylamide-free acid of 2-methyl-propyl phosphoric acid and the mixture of their salt and above-mentioned any compound.
Non-ionic monomer and anionic mol ratio B: F are between 95: 5 to 5: 95, and preferred described scope is 75: 25 to 25: 75, and more preferably described scope is 65: 35 to 35: 65, and most preferably described scope is 60: 40 to 40: 60.The molar percentage addition of B and F herein should be 100%.Also can comprise in the Formula I more than a kind of non-ionic monomer and anionic monomer.
In the embodiment of a first-selection of the present invention, the structure of water-soluble anionic multipolymer is seen Formula I, and wherein non-ionic polymers segment B is the repeating unit that forms behind the acrylamide polymerization; Anionic polymer chain section F is the repeating unit that forms after the acrylate polymerization.This preferred embodiment can be expressed from the next:
Figure A0282438800121
(Formulae II)
Wherein, M +Be positively charged ion (the preferred Na of acrylate +, K +Or NH 4 +), the mol ratio of B and F was from 75: 25 to 25: 75.
In another preferred embodiment of the present invention, M is Na in the Formulae II +, the segmental mol ratio of anionic moiety and nonionic is between 60: 40 to 40: 60.
Another aspect of the present invention is to adopt a kind of preparation method to make the synthetic water-soluble anionic copolymers possess the unique physical properties and the character of unanticipated.Because do not add linking agent in the preparation process, so the water-soluble anionic copolymers that obtains is not thought cross-linked polymer.A spot of linking agent can not have a strong impact on polymer property among the present invention.The unique distinction of the physical property of this water-soluble anionic copolymers is: record its Huggins constant greater than 0.75 in 0.01M NaCl solution, and the storage modulus G ' of described polymers soln of active substance that contains 1.5 weight % during 4.6Hz is greater than 175Pa (being preferably greater than 190, more preferably greater than 205).Huggins constant is preferably greater than 0.9, more preferably greater than 1.0 greater than 0.75.
Water-soluble anionic copolymers of the present invention is utilized the preparation of anti-phase (water-in-oil) emulsion polymerization technology.Those skilled in the art are familiar with this technology, for example can be with reference to United States Patent (USP) 3,284, and 393 and laid-open U.S. Patents 28,474 and 28,576 (being hereby incorporated by) again.Can prepare the aqueous solution by the anti-phase cause emulsion polymer that emulsion polymer is added in the entry, can also contain demulsifier surfactant in emulsion or the water herein.Demulsifier surfactant is to be added in the anti-phase additional surfactants of promotion in the emulsion.Resulting polymers also can be in organic solvent (as acetone) precipitate and separate and be dried to Powdered.This powder can be easy to be dissolved in the water-bearing media under the application scenario of needs.
Usually, the inverse emulsion polymerization process may further comprise the steps: 1) prepare monomeric aqueous solution, 2) aqueous solution is joined in the hydrocarbon liquids that comprises suitable tensio-active agent or surfactant mixture, thereby form anti-phase monomer emulsion, 3) this monomer emulsion carries out radical polymerization, 4) optionally add demulsifier surfactant, the emulsion when adding in the entry with promotion is anti-phase.
Letex polymerization can be undertaken by any way that those skilled in the art understand.Initiation can realize by heat or redox radical initiator (comprising azo-compound such as azobis isobutyronitrile and analogue).Polyreaction also can pass through photochemistry irradiation process, radiation or 60The Co ionizing rays realizes.
Preferred initiator is oil-soluble thermal initiator.Typical example includes but not limited to 2, and 2 '-azo is two-(2, the 4-methyl pentane nitrile), 2,2 '-azobis isobutyronitrile (AIBN), 2, and 2 '-azo is two-(2-methylbutyronitrile), 1,1 '-azo two (cyclohexanenitrile); Benzoyl peroxide and lauroyl peroxide.
Chain-transfer agent known to those skilled in the art all can be used to control molecular weight.They include, but are not limited to lower alkyl alcohol such as Virahol, amine, mercaptan such as mercaptoethanol, phosphite, thioic acid sulfoacid, allyl alcohol etc.
Typical aqueous solution comprises the aqueous mixture of a kind of non-ionic monomer or multiple non-ionic monomer mixture, anionic monomer or anionic monomer.Contain the conventional additives that water can also comprise needs.For example, may comprise sequestrant, pH regulator agent, initiator, aforesaid chain-transfer agent and other conventional additives in the mixture.PH value of aqueous solution preferably is equal to or greater than 2, more preferably between about 4 to about 6 less than 7 during the preparation water-soluble anionic copolymers.
Typical hydrocarbon liquids comprises straight chain hydrocarbon, branch chain hydrocarbon, saturated cyclic hydrocarbons, aromatic hydrocarbon or their mixture.
Used tensio-active agent of the present invention or surfactant mixture generally are oil-soluble.Can adopt one or more tensio-active agents.Tensio-active agent or surfactant mixture used among the present invention comprise at least a diblock or three block tensio-active agents.Option table surface-active agent or surfactant mixture and consumption thereof are to obtain the anti-phase monomer emulsion of polyreaction.Those skilled in the art understand these tensio-active agents, for example can be referring to " Hypermer  polymeric surfactant: the emulsifying agent that is used for reversed-phase polymerization ", ICI surfactant product handbook, ICI Americas Inc, 1997.Exemplary tensio-active agent comprises but is not limited to: polyoxyethylene-sorbitan mono-oleate (e.g., Atlas G-946, Uniqema, New Castle, DE), Arlacel-83, sorbitan trioleate, polyoxyethylene sorbitan monooleate, two-2-ethylhexyl sulfo-succinic acid, amine hydroxybenzene propyl-dimethyl amine, Unimac 5680-2-Sodium.alpha.-hydroxypropionate.Two blocks and three block polymerization tensio-active agents have been used among the present invention.Exemplary two blocks and three block polymerization tensio-active agents comprise but are not limited to: based on lipid acid and polyoxyethylene (as Hypermer  B246SF and IL-2595, two blocks of polyester derivatives Uniqema) and triblock copolymer, based on two blocks of polyoxyethylene and polyoxypropylene and triblock copolymer, based on polyisobutylene succinic anhydride and the polyoxyethylated pair of block and triblock copolymer, above-mentioned substance mixture and analogue thereof.Be preferably based on the two blocks and the triblock copolymer of lipid acid and polyoxyethylated polyester derivatives.When adopting three block tensio-active agents, this three block preferably includes two hydrophobic parts and a hydrophilic segment, and is promptly hydrophobic-hydrophilic-hydrophobic.Selecting one or more tensio-active agents is in order to make HLB value (hydrophilic hydrophobic balance value) between 2 to 8, preferably between 3 to 7, most preferably between 4 to 6.
The amount of binary and three block tensio-active agents (weight percentage) depends on the monomeric quantity of use.Binary and three block tensio-active agents and monomeric ratio were at least 3: 100.Binary and three block tensio-active agents and monomeric ratio can be greater than 3: 100, and preferred 4: 100, more preferably 5: 100, most preferably 6: 100.Binary and three block tensio-active agents are tensio-active agents main in the emulsion system.For the stability of improving emulsion with change its viscosity, can add second kind of tensio-active agent so that it is easy to handle and processing.The two or two kind of tensio-active agent comprises but is not limited to: the segmented copolymer of the ethylene oxide of fatty acid esters of sorbitan, ethoxyquin fatty acid esters of sorbitan, poly-ethoxyquin anhydro sorbitol lipid acid, alkylphenol and/or the ethylene oxide of propylene oxide affixture, long-chain alcohol or lipid acid and/or propylene oxide affixture, ethylene oxide/propylene oxide mixture, alkanolamine etc.
Inverse emulsion polymerization can be undertaken by any way that those skilled in the art understood, " contemporary polymer chemistry " (Englewood Cliffs, New Jersey, PRENTICE-HALL, 1981) that can write referring to Allcock and Lampe for example, the 3rd～5 chapter.
The invention provides a kind of cellulose fiber fiber products, it comprises cellulose fiber peacekeeping multipolymer of the present invention.
The present invention also provides a kind of method for preparing described cellulose fiber fiber products, comprises the step of adding multipolymer of the present invention in cellulose paste.
Multipolymer of the present invention can be used in paper manufacturing systems and the paper-making process.Described multipolymer can be used as draining and retention aid and contaminant conditioning agent.Cellulosic fibre slurry is deposited on the paper making wire cloth of motion in the paper process.Slurry may contain other additive such as sizing agent, starch, deposition control agent, mineral additive, pigment, filler, organic or inorganic flocculation agent, conventional flocculation agent or other pulp additive commonly used.Can form thin slice after removing the moisture in the deposition slurry.Usually thin slice is again through extruding and dry paper or the cardboard of forming.Thereby before slurry arrives silk screen, add multipolymer of the present invention and improve keeping of fiber fine powder and filler in draining or dehydration and the slurry.
Polymkeric substance among the present invention can stop pitch and the deposition of stickies on paper making equipment in magma or the recycle slurry as the contaminant conditioning agent.Auxiliary agent is added on the cohesion of disturbing pitch and stickies in the slurry, otherwise they can have destroying infection to paper, paper making equipment or paper-making process.
Suitable cellulosic fibre slurry comprises the chemical pulp that traditional paper making raw material is for example traditional in the inventive method, such as bleaching and unbleached sulfate pulp and sulfite pulp, mechanical pulp such as ground wood pulp, hot mechanical pulp, chemistry-Re mechanical pulp, recycle slurry as adopting old fluting board container, newsprinting paper, office waste, magazine paper and other not deinking waste product, deinking waste product and their mixture.
Multipolymer of the present invention can be used for final application in a variety of forms.Except that initial emulsion form, the multipolymer in the invention can also be made the aqueous solution, exsiccant pressed powder or form of suspension.Multipolymer in the invention generally will be diluted to the aqueous solution that contains 0.1～1% reactive polymer when using.
The dilute solution adding paper-making process of multipolymer of the present invention is influenced retention and drainage.The multipolymer of invention can join in dense or rare slurry, preferably adds in the grout.Described multipolymer can add at a reinforced place, perhaps adds at two or more different feed points simultaneously.Before typical feed point is included in fan pump, after the fan pump before the pressure pulp screen or after the pressure pulp screen.
Multipolymer usage ratio of the present invention cellulose paste preferably per ton uses about about 0.01 to 10 pound reactive polymer (being as the criterion with the slurry dry weight).Preferred copolymer concentration is 0.05 to 5 pound/ton (being as the criterion with the cellulose slurry dry weight).
Below in conjunction with a plurality of specific exampless the present invention is further described, these examples for illustrative purposes only usefulness and do not limit the scope of the invention.
Embodiment
Water-soluble anionic copolymers and relatively use multipolymer
Embodiment 1
Polymeric amide acrylamide reversed-phase emulsion
In a suitable reaction flask that overhead mechanical stirrer, thermometer, nitrogen bubble pipe and condenser be housed, add paraffin oil phase (135.0g, Exxsol D80 oil, Exxon-Huouston, TX) and tensio-active agent (4.5g, Atlas G-946 and 9.0gHypermer B246SF).Then the temperature of oil phase is adjusted to 37 ℃.
The aqueous solution, 68.7g vinylformic acid, 70.0g deionized water and 0.7g Versenex 80 (Dow chemical) the intercalating agent formulations prepared from solutions that contains 53 weight % acrylamides with 126.5g goes out water.Add ammonia soln (33.1g, NH then 3Content 29.4 weight %) the pH value of adjusting water is 5.4.The temperature of neutralization back water is 39 ℃.
Water is added oil phase, in homogenizer, mix obtaining stable water-in-oil emulsion simultaneously.Then emulsion is mixed with a quaterfoil glassed agitator, blasted nitrogen simultaneously 60 minutes.When feeding nitrogen, the temperature of emulsion is transferred to 50 ± 1 ℃.Then, stop to blow, charge into nitrogen blanket.
The 3 weight % solution of AIBN in toluene that added 0.213g in two hours come initiated polymerization.The initiation AIBN of this correspondence is all monomeric 250ppm.In the process of adding, the temperature of reaction mixture can be raised to 62 ℃ (about 50 minutes), and the temperature with reaction mixture remains on 62 ± 1 ℃ then.After the interpolation, the temperature of reaction mixture is remained on 62 ± 1 ℃, continue 1 hour.The 3 weight % solution of AIBN in toluene that in one minute, add 0.085g then.The initiation AIBN of this correspondence is all monomeric 100ppm.Then reaction mixture was kept 2 hours at 62 ± 1 ℃, then cool to room temperature is collected product then.
Except at table 1 with mention hereinafter, embodiment 2-13 and Comparative Examples 1-11 adopt the method for embodiment 1 to prepare multipolymer.
Embodiment 2-4
Except the pH value of water is respectively 3.0,4.0 and 6.0, the method preparation of embodiment 2-4 by describing among the embodiment 1.
Comparative Examples 1 and 2
Except the pH value of water is respectively 7.1 and 8.0, the methods preparation of Comparative Examples 1 and 2 by describing among the embodiment 1.The storage modulus G ' of these two kinds of products is respectively 115 and 36Pa, all less than threshold value 175Pa of the present invention.
Embodiment 5-6
Except the weight ratio of Atlas G-946 and Hypermer  B246SF tensio-active agent is adjusted into respectively 2: 1 and 1: 1, the methods preparation of embodiment 5 and 6 by describing among the embodiment 1.
Embodiment 7-9
Except the variation of the surfactant system shown in the table 1, the method preparation of embodiment 7-9 by describing among the embodiment 1.
Comparative Examples 3 and 4
What particularly point out is that the promoting agent that uses in the organic microballoon of preparation in surfactant system that uses in Comparative Examples 3 and 4 and the United States Patent (USP) 5,167,766 and 5,274,055 is identical.In Comparative Examples 3, the hydrophilic-hydrophobic balance value of used promoting agent is greater than 8.In Comparative Examples 4, the pH value that needs to contain water is adjusted to 7.0 and is obtained stable emulsion.Clearly, tensio-active agent and/or the initiator composition final product that is not enough to obtain expecting (G '＞175Pa and k '＞0.75).
Embodiment 10
Except the initiator system shown in the table 1 changes, the method preparation of embodiment 10 by describing among the embodiment 1.Initiated oxidation agent in the present embodiment (tertbutyl peroxide) once all drops into, and causes reductive agent (Sodium Pyrosulfite) and then dropwise adds reactor.The adding of reductive agent continues 3.5 hours.
Comparative Examples 5 and 6
For Comparative Examples 5, the initiated oxidation agent (cumene hydroperoxide) that in 5 minutes, adds 25ppm (based on monomeric total amount), in the time more than 3 hours, add the reductive agent (Sodium Pyrosulfite) of 25ppm (based on monomeric total amount) again, left standstill then 45 minutes.The oxygenant of disposable then adding 50ppm and the reductive agent of 50ppm (based on monomeric total amount), then material kept 2 hours in about 50 ℃ temperature of reaction.
In Comparative Examples 6, initiated oxidation agent (potassium bromate) is added in the material fast, then the time of reductive agent (Sodium Pyrosulfite) with more than 3 hours is added, left standstill then 45 minutes.Disposable then adding Oxidizing and Reducing Agents, then material kept 2 hours in about 50 ℃ temperature of reaction
Comparative Examples 7-10
Except will the material amount be 10,50,250 thoroughly, the N,N methylene bis acrylamide (MBA) of 2000ppm adds the aqueous phase method preparation of Comparative Examples 7-10 by describing among the embodiment 1 with respect to total monomer.MBA is a kind of linking agent, is not comprised product in the present invention.
Embodiment 11-12
Except the mol ratio of vinylformic acid and acrylamide is respectively 60: 40 and 40: 60, the methods preparation of embodiment 11 and 12 by describing among the embodiment 1.
Embodiment 13
Except initial reaction temperature is 57 ℃, be incubated 8 hours outside (during this period, preceding two initiators added at the 0th and the 360th minute), the method preparation of embodiment 13 by describing among the embodiment 1.Temperature is adjusted to 65 ℃ then, be incubated 2.5 hours.Third and fourth initiator is in adding in the 0th and the 30th minute of second section soaking time.Aqueous sodium hydroxide solution is also replaced by equimolar ammonium hydroxide.
Table 1: preparation condition
Embodiment Form acrylic acid acrylamide water pH Surfactivity combination weight % surface ratio (always) promoting agent Ppm content with respect to total initiator amount of monomer Explanation
????1 ??50.0％??????50.0％???????5.4 ??3.0％??????????????G-946∶B246SF??1∶2 ????AlBN????2507100
????2 ??″??????????″???????????3.0 ??″?????????????????″?????????????″ ????″??????″
????3 ??″??????????″???????????4.0 ??″?????????????????″?????????????″ ????″??????″
????4 ??″??????????″???????????6.0 ??″?????????????????″?????????????″ ????″??????″
Comparative Examples 1 ??″??????????″???????????7.1 ??″?????????????????″?????????????″ ????″??????″
Comparative Examples 2 ??″??????????″???????????8.0 ??″?????????????????″?????????????″ ????″??????″
????5 ??″??????????″???????????5.4 ??″?????????????????″?????????????2∶1 ????″??????″
????6 ??″??????????″???????????″ ??″?????????????????″?????????????1∶1 ????″??????″
????7 ??″??????????″???????????″ ??″????????????????Sesquioleate∶??1∶2 ????″??????″
????8 ??″??????????″???????????″ ??″????????????????G-946∶B206?????″ ????″??????″
????9 ??″??????????″???????????″ ??″????????????????G-946∶IL-2595??″ ????″??????″
Comparative Examples 3 ??″??????????″???????????″ ??″????????????????POEHEX∶????????85∶15 ????????????????????Sesquioleate ????″??????″
Comparative Examples 4 ??″??????????″???????????7.0 ??″????????????????G-946???????????100 ????″??????″
????10 ??″??????????″???????????5.4 ??″????????????????G-946∶B246SF???1∶2 ????t-BHP???25 ????SMBS????25
Comparative Examples 5 ??″??????????″???????????″ ??″????????????????″??????????????″ ????CHP?????25/25 ????SMBS????50/50
Comparative Examples 6 ??″??????????″???????????″ ??″????????????????″??????????????″ ????KBrO3???25/25 ????SMBS????50/50
Comparative Examples 7 ??″??????????″???????????″ ??″????????????????″??????????????″ ????AlBN????250/100 10ppm MBA
Comparative Examples 8 ??″??????????″???????????″ ??″????????????????″??????????????″ ????″??????″ 50ppm MBA
Comparative Examples 9 ??″??????????″???????????″ ??″????????????????″??????????????″ ????″??????″ 250ppm MBA
Comparative Examples 10 ??″??????????″???????????″ ??″????????????????″??????????????″ ????″??????″ 2,000ppm MBA
????11 ??60.0％??????40.0％???????″ ??″????????????????″??????????????″ ????″??????″
????12 ??40.0％??????60.0％???????″ ??″????????????????″??????????????″ ????″??????″
????13 ??50.0％??????50.0％???????″ ??″????????????????″??????????????″ ????″??????10/10/257 ????????????100 Feed in raw material for 4 times altogether
Amount of initiator is the molar ppm content than total amount of monomer.
Composition is monomeric molar percentage.
Atlas G-946=polyoxyethylene-sorbitan mono-oleate (Uniqema-New Castle, DE) B246SF=Hypermer  B246SF (Uniqema-New Castle, DE) (based on the triblock polymer of the polyester derivatives of oxystearic acid and 1500 molecular weight polyisoprene ethylene glycol) Sesquioleate=Arlacel-83 (Aldrich-Milwaukee, W1) B206=Hypermer  B206 (Uniqema-New Castle, DE) (based on the triblock polymer of the polyester derivatives of oxystearic acid and 600 molecular weight polyisoprene ethylene glycol).
IL-2595=Hypermer  IL-2595 (Uniqema-New Castle, DE) (based on the triblock polymer of the polyester derivatives of oxystearic acid and 1000 molecular weight polyisoprene ethylene glycol).
(HLB 10.2, Aldrich) for POEHEX=polyoxyethylene groups anhydro sorbitol hexyl oleic acid ester.
AIBN=2,2 '-Diisopropyl azodicarboxylate (Wako-Richmond, VA).
The t-BHP=tertbutyl peroxide (Aldrich-Milwaukee, W1).
The SMBS=Sodium Pyrosulfite (Aldrich-Milwaukee, W1).
The CHP=cumene hydroperoxide (Aldrich-Milwaukee, W1).
KBrO 3=Potassium Bromide (Aldrich-Milwaukee, W1).
Ppm MBA=N, the N-methylene-bisacrylamide with respect to the molar ppm content of total monomer amount (Aldrich-Milwaukee, W1).
The rheological property of water-soluble anionic copolymers and contrast multipolymer
Table 2 is water-soluble anionic copolymers embodiment commercially available retention and draining additive (table look-ups of the rheological characteristics of Polyflex CP.3 (Ciba-Tarrytown, NY)) with respect to standard.(Chemtall-Riceboro GA) also is used as comparison: EM 635, AN 956 VLM, AN 956 and AN 956 VHM to four kinds of anionic polyacrylamides commonly used (APAM)." EM " refers in particular to the reversed-phase emulsion product, and " AN " refers in particular to power-product.It is that 50: 50 sodium acrylate and acrylamide formed that these contrast APAM products it is reported all by mol ratio.The relative molecular weight size order of AN series is: AN 956 VLM＜AN 956＜AN 956 VHM.
In that the water-soluble anionic copolymers emulsion is anti-phase with before analyzing, the demulsifier surfactant that adds about 2 weight %, Tergitol 15-S-9 (Dow-Midland for example, M1) and Aerosol-OT-S (Cytec Industries-West Patterson is NJ) by the mixture of 80: 20 weight ratios.Then the pH value of anti-phase water-soluble anionic copolymers is adjusted to minimum value 7.0 with sodium hydroxide or ammonium hydroxide aqueous solution.
" rheology: principle, measurement and application " (New York, Wiley, 1994) of Macosko, " polymer science basis " (New York of L.H.Sperling, Wiley-lnterscience, 1992) and J.Ferry " viscoelastic property of polymkeric substance " (the 3rd edition, New York, J.Wiley ﹠amp; Sons, 1980) provide discussion to these rheological techniques.Visco-elasticity discussed here is to be to applying the time-dependent relation of outer force-responsive, and material will show hard or vitrified behavior when short period of time or high frequency, and material can flow when long-time or low frequency, the performance adhering performance.(1.5%, determine to the solution of polymkeric substance in deionized water by measurement w/w) by using the controlled stress rheometer of Haake RS-75 for viscoelastic property.Frequency sweeping is produced by the dynamic concussion pattern of rheometer, and constant stress is at linear viscoelastic region, and frequency is from 0.01Hz to 10Hz.The output result of test will determine the elastic part (or the energy of concussion cycle storage) at every turn of material and viscosity partly (or the energy of phase loss) weekly.Storage modulus (G ') is defined as follows:
G′(Pa)＝(τ 0/γ 0)cosδ
Out-of-phase modulus is defined as follows:
G″(Pa)＝(τ 0/γ 0)sinδ
Wherein, τ 0Be stress amplitude, γ 0Be the maximum strain amplitude, δ is that the phase angle between the stress and strain is poor.
Get in terminal (low frequency range), because have the sufficiently long time to allow the chain of polymkeric substance to unclamp and mainly embody viscous behavior, the out-of-phase modulus of linear polymer is greater than storage modulus.Work as increase frequency, the rubber-like platform area occurred, polymer chain unclamps the needed time greater than the test duration.In this zone, storage modulus is greater than out-of-phase modulus, and material is shown as the network of being made up of permanent winding.Storage modulus is irrelevant with test frequency in this zone.This modulus is the function by the network node concentration of rubber elasticity theory definition.
G N＝nRT
Wherein, G NBe the platform modulus, n is the concentration of network node, and R is a gas law constant, and T is a temperature.
Can think approaching in size in platform area platform modulus with storage modulus.When the concentration increase of network node, modulus will increase.These network nodes are subjected to the influence of chemistry or physical crosslinking.As shown in table 2, material of the present invention is higher than the linear APAM flocculation agent EM635 of equivalent at the storage modulus G ' of 4.6Hz, and this shows and has associating network node.
The performance of dilute solution has provided the indication that polymer flow body dynamics volume (HDV) and molecular weight are associated.In this experiment, to solvent viscosity (η 0) compare with polymers soln viscosity (η).Specific viscosity (η Sp) provide by following formula, be the ratio of no unit.
η sp＝(η/η 0) -1
The specific viscosity of reduction (RSV) is that specific viscosity is divided by concentration.Intrinsic viscosity [η] (or IV) be when concentration is tending towards 0 specific viscosity divided by the value of polymer concentration.
[η]＝[η sp/c] c→0
The unit of IV is decilitre every gram (dL/g), the hydrokinetics volume of expression polymkeric substance in solution.Therefore high IV value shows hydrokinetics volume big in the solution; When comparing with the conventional polymer of similar composition in the similar solvent, high IV value shows higher molecular weight.The measuring condition of IV value is in the table 2: in 0.01M NaCl solution, from 0.0025% to 0.025%, 30 ℃ of the concentration of dilution is used Ubbelohde type " 0C " rheometer.
The Huggins constant of no unit (k ') obtain according to following formula by the slope of IV data:
η sp/c＝[η]+k′[η] 2c
Wherein, the value of c is between 0.0025 weight % and 0.025 weight %.
Editors such as Mark are at " polymer science and engineering encyclopedia " (New York, J.Wiley ﹠amp; Sons, 1988) first roll is mentioned for 26 to 27 pages, and the typical k ' value of linear polymer is in approximate 0.25 to 0.50 scope.K ' increases the increase show polymkeric substance " structure ", can give the credit to comprise and associating or a lot of influence factors of crosslinked polymer architecture.K ' the value of table 2 neutral line APAM is 0.3 to 0.4, and the k ' of the preferred water-soluble anionic copolymers of the present invention value has further been supported the existence of nonlinear substance greater than 0.75.
Viscosity-average molecular weight Mv is obtained by the reduction specific viscosity value of 0.025% polymkeric substance that is dissolved in 1M NaCl (wherein also comprising 0.1%Surfonic  N-95 tensio-active agent (Chevron Texaco, San Francisco)).Mv is obtained by reduction specific viscosity value/Mv typical curve that the conventional APAM with the known molecular amount sets up.Mv in the table should be considered to have the Mv value of the linear APAM of the reduction specific viscosity identical with polymer samples.Because it is destroyed that association does not have under the situation of 0.1%SurfonicN-95 tensio-active agent, real Mv value might be higher than listed value.
Table 2
Embodiment G′，4.6Hz ???Pa Intrinsic viscosity dL/g Huggins constant k ' ????Mv ??g/mole
???1 ??260 ????41 ????2.2 ????8.0
234 Comparative Examples, 1 Comparative Examples 2 ??237 ??236 ??205 ??115 ??36 ????32 ????32 ????43 ????68 ????47 ????2.0 ????2.5 ????1.9 ????0.7 ????1.5 ????3.1 ????3.0 ????7.6 ????13.5 ????4.2
???5 ???6 ??312 ??369 ????29 ????37 ????2.2 ????2.3 ????6.2 ????4.6
789 Comparative Examples, 3 Comparative Examples 4 ??310 ??315 ??290 ??130 ??136 ????38 ????30 ????39 ????82 ????88 ????1.8 ????1.7 ????2.2 ????0.6 ????0.2 ????5.6 ????3.3 ????6.6 ????16.7 ????20.7
10 Comparative Examples, 5 Comparative Examples 6 ??189 ??133 ??154 ????50 ????50 ????50 ????1.1 ????1.0 ????1.0 ????12.9 ????8.0 ????9.8
Comparative Examples 7 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 ??745 ??1,869 ??4,230 ??6,539 ????15 ????10 ????2 ????1 ????12.0 ????3.3 ????28.0 ????N/A ????1.5 ????0.6 ????0.2 ????N/A
???11 ???12 ??328 ??237 ????42 ????41 ????2.3 ????1.1 ????6.6 ????7.6
???13 ??198 ????46 ????1.9 ????5.6
???Polyflex?CP.3 ??383 ????32 ????1.0 ????N/A
???AN?956?VLM ???AN?956 ???AN?956?VHM ???EM?635 ??31 ??75 ??87 ??130 ????20 ????60 ????80 ????90 ????0.3 ????0.4 ????0.4 ????0.3 ????3.8 ????12.0 ????17.0 ????23.0
G ' storage modulus (Pa)=at 25 ℃, 4.6Hz, 1.5% (w/w) polymkeric substance.
Intrinsic viscosity IV (dL/g):, among the 0.01M NaCl, use Ubbelohde type " 0C " viscometer at 30 ℃.
The Huggins constant of k '=obtain from the IV data
Mv=is by the viscosity-average molecular weight that reduction specific viscosity value/the Mv typical curve obtains of the linear APAM of known molecular amount
For embodiment 17-20, because the existence of linking agent causes low IV value, the k ' that calculates is not quite credible.
Performance test
Those skilled in the art are shaped to the scraps of paper and keep chemical technology and know very much." paper pulp and paper ordinary artisan handbook (the Atlanta GA that writes referring to G.A.Smook for example, TAPPI Press, 1989) and J.P.Casey " paper pulp and paper: chemistry and the chemical technology " third edition (New York, Wiley-lnterscience, 1981) of writing.
In order to estimate the performance of water-soluble anionic copolymers sample of the present invention, carried out the Britt jar and kept test and Canadian Standard Freeness (CSF) drainage test, and compared with Polyflex CP.3 (Ciba) (a kind of) generally at the drained organic water auxiliary agent of industrial being called as " little polymkeric substance ".In order more also four kinds of conventional anionic polyacrylamides (Chemtall) also to have been carried out performance evaluation: EM 635, AN 956 VLM, AN 956 and AN 956 VHM.Unless otherwise indicated, all per-cents, ratio etc. all are by weight.
For each embodiment, multipolymer is mixed with a kind of standard cation polyacrylamide, then test.Use similar methods, copolymer sample is mixed with a kind of standard anionic polyacrylamide/sodium acrylate.Copolymer sample adds with the ratio of 0.4 pound of activeconstituents/ton furnish solids.Thus, with the effectiveness of multipolymer of the present invention and contrast multipolymer with do not add the negatively charged ion of multipolymer of the present invention and positively charged ion is kept or the draining prescription compares.Be the description of test process below.
The batching of using in test process is artificial alkalescence batching.This batching is to be made by commercially available lapped pulp, water and other material that the drying of hardwood and cork is crossed.(W1) the commercially available lapped pulp of respectively drying of hardwood and cork being crossed carries out refining for Voith, Appleton at first to use laboratory Valley hollander.Then these paper pulp are added in the water-bearing media.
The used water-bearing media of preparing ingredients comprises that the mixture of local hard water and deionized water reaches a typical hardness.Adding a large amount of inorganic salt makes this medium have typical alkalescence and solution conductivity.
In order to prepare this batching, hardwood and cork are distributed in the water-bearing media with specific weight ratio.The precipitated chalk (PCC) of 25 weight % (based on the paper pulp dry weight) is added in the batching, thereby make final batching comprise 80% fiber and 20% PCC stopping composition.
The positively charged ion potato starch that uses be Stalok 400 (A.E.Staley, Decatur, IL), alum be 50% octadecyl alum liquor (Delta Chemical Corporation, Baltimore, MD).
In standard cation polyacrylamide treating processes (be called for short CPAM) cationic flocculant of use be molar content be acrylamide/acryl trimethyl ammonium chloride of 90/10% (Perform PC 8138, Hercules).In standard anionic polyacrylamide treating processes (be called for short APAM) the negatively charged ion flocculation agent of use be molar content be acrylamide/sodium acrylate copolymer of 70/30% (Perform PA 8137, Hercules); Described flocculation agent can have been bought on the market, is from anti-phase water-in-oil emulsion.Water-soluble anionic copolymers and contrast multipolymer are added with 0.4 pound/ton ratio in the benchmark treatment formulations of " 0.4#CPAM ", and it comprises 10 pounds/ton the alum of 400,5 pounds/ton of Sta-Lok and 0.4 pound/ton Perform PC 8138.The benchmark treatment formulations of " 0.2#APAM " comprises the alum of 10 pounds/ton 400,5 pounds/ton of Sta-Lok, 0.2 pound/ton PC 8137.
The Britt jar is kept test, and (paper industry research material company, Gig Harbor WA) is being known in the art.In keeping test, the batching of designated volume is mixed under dynamic condition, and the mesh screen of pot bottom is crossed in the materials flow of equivalent, can determine the content of fine particle materials thus.The Britt jar that this test is used has installed 3 turbulization blended blades on cylindrical wall, the mesh screen of 76 μ m has been used in the bottom.
To the solid concentration of about 500ml is that 0.5% synthetic batching is carried out the Britt jar and kept test.Under the 1200rpm rotating speed, add starch, alum, polymkeric substance flocculation agent and drainage aids successively; All material is mixed specified pitch time.After adding water discharge agent and mixing, collect filtrate.
The retention that calculates is the fine particle retention, at first measures fine grain total content in the batching: wash about 500 milliliters batching with 10 premium on currency under agitation condition, to remove wherein all less than the fine particle of Britt jar 76 μ m mesh screens.To determine the fine particle retention that each is handled through the filter paper of the 100ml filtrate of above-mentioned processing 1.5 μ m by weighing up weight in advance.The fine particle retention calculates according to following formula
% fine particle retention=(filtrate weight-fine particle weight)/filtrate weight.
Wherein, filtrate and fine grain weight all normalize to 100ml.The retention that obtains is the average of twice repeated experiments result.
The CPAM of the water-soluble anionic copolymers sample of 0.4 pound of/ton paper pulp and comparative sample and 0.4 pound of/ton paper pulp is carried out the Britt jar keep test.
CSF equipment (Lorentzen ﹠amp; Wettre, Code 30, Stockholm, Sweden) be used for measuring relative drainage rates or rate of water loss, also known (TAPPI TestProcedure T-227) in this area by the people.CSF equipment comprises a drain chamber and a velocity survey funnel, and they all are installed on the proper supporting thing.Drain chamber is a cylindricality, in the sieve plate of perforation is arranged, a hinge plate is arranged at the bottom, a vacuum-packed hinged lid is arranged at the top.The velocity survey funnel has base apertures and side overflow weir.
Adopt the CSF drainage test that the batching of 1 liter of solids content 0.30% is tested.One outside CSF equipment provides the batching that preparation is used for described operation in the turbulent flow blended square opening cup, adopts and identical speed and the churning time of Britt jar test.After the adding of finishing additive and mixing, the batching of handling is poured into drain chamber, close top cover, then open base plate rapidly.Water can enter in the funnel that tests the speed unobstructedly; The current that exceed the bottom outlet flux will overflow by side opening, are collected in the graduated cylinder then.The value that produces uses milliliter filtrate to explain; High more draining or the degree of dehydration of showing of numerical value is high more.
Listed Britt jar value of keeping and CSF value have provided the difference of compound sample on the value of keeping and drain value of CPAM or APAM processing in table 3.Keep in test and the CSF drainage test at the Britt jar, the improvement value is high more to be shown that activity is high more and responds and unreasonablely think.
Table 3
??Ex. 0.4#CPAM Britt jar % fine particle retention 0.4#CPAM CSF ml increment 0.2# APAM CSF ml increment
??1 ????30.0 ????200 ????155
234 Comparative Examples, 1 Comparative Examples 2 ????28.0 ????27.5 ????31.5 ????23.9 ????5.6 ????190 ????180 ????205 ????165 ????145 ????150 ????140 ????160 ????120 ????105
??5 ??6 ????27.0 ????30.0 ????180 ????200 ????135 ????150
789 Comparative Examples, 3 Comparative Examples 4 ????31.5 ????19.7 ????30.0 ????28.0 ????27.0 ????210 ????120 ????175 ????200 ????205 ????160 ????95 ????135 ????165 ????165
10 Comparative Examples, 5 Comparative Examples 6 ????27.3 ????25.9 ????27.9 ????195 ????200 ????200 ????155 ????150 ????150
Comparative Examples 7 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 ????20.1 ????22.3 ????8.4 ????-20.0 ????160 ????140 ????95 ????60 ????130 ????100 ????60 ????-10
??11 ??12 ????29.5 ????32.9 ????200 ????200 ????150 ????155
??13 ????30.0 ????205 ????155
??Polyflex?CP.3 ????30.0 ????200 ????150
??AN?956?VLM ??AN?956 ??AN?956?VHM ??EM?635 ????0.0 ????15.0 ????18.0 ????20.0 ????120 ????160 ????185 ????190 ????70 ????120 ????130 ????135
Data in the table 3 have provided water-soluble anionic copolymers of the present invention and Polyflex CP.3 as a comparison, the anionic polyacrylamide of routine and keeping/draining activity (R/D) of Comparative Examples.Usually for G-946/B246SF tensio-active agent+AIBN initiator system, total R/D activity (embodiment 1,4,5 and 6) and to increase B246SF content (embodiment 1,5 and 6) in combinations-of surfactants be optimum when containing aqueous pH values at 5-6.For other initiator and/or surfactant system, the R/D activity can be compared with anionic polyacrylamide commonly used with Polyflex CP.3, shows still low generally many R/D activity of increase except embodiment 8.
Also carried out a series of keeping and drainage test with vacuum drainage test method(s) (VDT), this experiment is used to the activity of comparison microballoon technology and conventional linear flocculants.Test-results shows that VDT can come drainage aids in the CPAM of comparison and the APAM process with the length of water discharge time.
The B test of describing in the book of reference of this equipment configuration and a lot of filtration aspects (for example " Perry chemical industry handbook, the 7th edition, McGraw-Hill, New York, 1999, page number 18-78) is similar.VDT has the vacuum pump of vacuumometer and setter to constitute by a 300ml magnetic Gelman filter funnel, 250ml graduated cylinder, rapid-acting coupling, water trap and one.The VDT process of the test is as follows: earlier vacuum is set to designated value (general 10 inches of mercury), correctly is placed on funnel on the cylinder; Then the paper making raw material with the 0.5 weight % of 250g adds in the beaker, requires under the stirring of overhead additive (as starch, alum, flocculation agent to be measured) to be added in the raw material according to handling procedure then.Pour raw material into filter funnel then, open vacuum pump, open stopwatch simultaneously.Drainage efficiency characterizes with obtaining the used time of 230ml filtrate.
The principle of VDT is based on filtrate cake theory, " solid-liquid separation " the 9th chapter that can write referring to L.Svarovsky, the third edition (London, Butterworths, 1990).In when beginning, the deposition of solids in the slurry relative thin be used for support on the filtration medium of filter cake.The continuous formation of deposits of solid layer filter cake or filter bed.The speed of filtrate by filter cake (or filter bed) is decided by throw out density, throw out distribution of sizes and the amount that contains the residual polymer materials of aqueous phase on mat.The throw out and the low flocculation agent of the residual quantity in water that can form fine and close consistent size can show good drainage in the VDT test, vice versa.
The VDT of the APAM process of same recipe estimated the activity that obtains during listed data declaration water-soluble anionic copolymers use of the present invention was tested with CSF in the table 4.The consumption of relevant starch, alum and negatively charged ion flocculation agent was as described in Table 3 during described benchmark was handled.Experiment and Comparative Examples are formed with 0.4 pound/ton activation and are estimated.The difference of sample water discharge time was thought effectively on statistics greater than 1.0 seconds.
Table 4
Embodiment 0.4 pound/ton VDT (sec)
????1 ????21.3
234 Comparative Examples, 1 Comparative Examples 2 ????22.1 ????22.5 ????21.2 ????23.7 ????27.0
????5 ????6 ????22.0 ????20.6
789 Comparative Examples, 3 Comparative Examples 4 ????20.5 ????24.9 ????27.5 ????22.4 ????23.6
10 Comparative Examples, 5 Comparative Examples 6 ????21.9 ????23.6 ????22.2
Comparative Examples 7 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 ????23.0 ????24.2 ????27.0 ????33.0
????11 ????12 ????21.0 ????20.3
????13 ????20.6
????Polyflex?CP.3 ????20.0
????AN?956?VLM ????AN?956 ????AN?956?VHM ????EM?635 ????28.6 ????25.0 ????26.2 ????25.6
The no draining control agent of control experiment ????32.0
Data in the table 4 show water-soluble anionic copolymers of the present invention, Polyflex CP.3 and the difference of conventional anionic polyacrylamide flocculation agent on water discharge time length.Polyflex CP.3 has fast drainage speed, and the characteristics of conventional anionic polyacrylamide flocculation agent are much lower drainage speeds.Generally speaking, for the water-soluble anionic copolymers of using G-946/B246SF surfactant composition and AIBN initiator composition to prepare, because sample shows the R/D activity of optimization in table 3, their performance trend can be compared with Polyflex CP.3.The VDT of Comparative Examples response significantly reduces greater than the increase of 6 increase and MBA along with containing aqueous pH values.Comparative Examples polymkeric substance by optional surfactant system (Comparative Examples 3 and 4) and initiator system (Comparative Examples 5 and 6) preparation demonstrates the weak VDT draining response similar to conventional anionic polyacrylamide.
Generally speaking, the tensio-active agent initiator system that use has emulsifying effect goes out water-soluble anionic copolymers with some combinations produce that contains aqueous pH values, it is characterized in that k ' is greater than 0.75, G ' is greater than 175Pa, and R/D unexpectedly can compare with the organic microballoon technology of Polyflex CP.3 with the shaping activity.
The preferred water-soluble anionic copolymers of the present invention prepares by using the inverse emulsion polymerization technology, and it uses a kind of emulsifying surfactant that comprises A-B or A-B-A polymeric surfactant, the water of pH value 2 to 7 and oil soluble radical initiator.
Particularly preferred water-soluble anionic copolymers is by the preparation of inverse emulsion polymerization technology, use Hypermer  B246SF or IL-2595 and dehydrated sorbitol mono-fatty acid ester to make up as the emulsification surfactant, the pH value is 3 to 6 the water that contains, and using 2,2 '-azobis isobutyronitrile (AIBN) is as radical initiator.
What particularly point out is that aforesaid example usefulness for illustrative purposes only must not be interpreted as limitation of the present invention.Invention has been described in conjunction with the embodiments above, yet be understood that: literal used herein is descriptive and illustrative, rather than restrictive.Under the situation that does not depart from the scope of the invention and flesh and blood, can make amendment within the scope of the appended claims and improve.Although invention has been described in conjunction with concrete method, material and example at this, yet the present invention is not limited to details disclosed herein.For example, positively charged ion and/or the amphoteric multipolymer through preferred polymerizing condition preparation also can show unique activity in papermaking is used.Water-soluble anionic copolymers liquid of the present invention can use at other (for example in wastewater treatment as condensing agent or flocculation agent, perhaps in boring or cement treated are used as rheological characteristics properties-correcting agent) show unique activity.

Claims (29)

1, water-soluble anionic copolymers, it has following chemical formula:
[-B-co-F-]
Wherein B is the non-ionic polymers segment that is formed by the unsaturated non-ionic monomer polymerization of one or more vinyl;
F is the anionic polymer chain section that is formed by the unsaturated anionic monomer polymerization of one or more vinyl;
The molar ratio range of B and F was from 95: 5 to 5: 95; And
Described water-soluble anionic copolymers is by the preparation of water-in-oil emulsion polymerization technique, used at least a emulsifying surfactant that comprises at least one two block or triblock polymer surfactant, wherein at least one two block or triblock polymer surfactant and monomeric ratio were at least 3: 100;
Wherein said invert emulsion polymerization technique comprises following steps:
Prepare the monomeric aqueous solution,
The described aqueous solution added in the hydrocarbon liquids that comprises tensio-active agent or surfactant mixtures produce reversed-phase emulsion, make monomer generation polymerization emulsion by the radical polymerization effect from 2 in less than 7 scope in the pH value; Wherein containing the multipolymer Huggins constant that 0.0025 weight % records in the 0.01M NaCl solution of the described multipolymer of 0.025 weight % (k ') greater than 0.75; And contain the described copolymer solution of 1.5 weight % activess in the storage modulus of 4.6Hz (G ') greater than 175Pa.
2, multipolymer as claimed in claim 1, wherein B is selected from acrylamide, Methacrylamide; N-alkyl acrylamide, N, N-dialkyl group-acrylamide; Methyl methacrylate, methyl acrylate; Vinyl cyanide; N-vinyl methylacetamide; N-vinyl methylformamide; Vinylacetate; The N-vinyl pyrrolidone; And the mixture of above-mentioned any compound.
3, multipolymer as claimed in claim 1, wherein F is selected from vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, acrylamide oxyacetic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid, the 2-acrylamide-free acid of 2-methyl-propyl phosphoric acid and the mixture of their salt and above-mentioned any compound.
4, multipolymer as claimed in claim 1, the wherein said pair of block or three block tensio-active agents are based on the multipolymer of lipid acid and polyoxyethylated polyester derivatives.
5, multipolymer as claimed in claim 1, wherein the pH value from about 3 to about 6.
6, multipolymer as claimed in claim 1 wherein uses 2, and 2 '-azobis isobutyronitrile is as radical initiator.
7, multipolymer as claimed in claim 1, wherein two blocks or three block tensio-active agents and monomeric mol ratio were at least 4: 100.
8, multipolymer as claimed in claim 1, wherein the HLB of emulsifying surfactant combination is less than 8.
9, multipolymer as claimed in claim 1, wherein said non-ionic polymers segment B is an acrylamide, described anionic polymer chain section F is selected from acrylic acid sodium salt, sylvite and ammonium salt.
10, multipolymer as claimed in claim 1, wherein said tensio-active agent comprises: a) a kind of pair of block or three block tensio-active agents, it comprises the water-soluble portion that derives from the compound monocarboxylic part of oil soluble and derive from polyalkylene glycol, and b) a kind of sorbitan fatty acid esters; The pH value that contains water is 3 to 6; And use 2,2 '-azobis isobutyronitrile is as radical initiator.
11, a kind of composition that comprises the described polymkeric substance of cellulose fiber peacekeeping claim 1.
12, a kind of composition that comprises the described polymkeric substance of cellulose fiber peacekeeping claim 9.
13, composition as claimed in claim 11, wherein said cellulosic fibre is a pulp.
14, composition as claimed in claim 11, wherein said cellulosic fibre are paper or cardboard.
15, a kind of method of making the cellulose fiber fiber products, described method comprise the described water-soluble anionic copolymers of claim 1 are added in the cellulose pulp slurry.
16, method as claimed in claim 15, wherein said emulsifying surfactant comprises: a) a kind of pair of block or three block tensio-active agents, it comprises the water-soluble portion that derives from the compound monocarboxylic part of oil soluble and derive from polyalkylene glycol, and b) a kind of sorbitan fatty acid esters; The pH value that contains water is 3 to 6; And use 2,2 '-azobis isobutyronitrile is as radical initiator.
17, method as claimed in claim 15, wherein B is an acrylamide, F is a kind of acrylate, the mol ratio of vinylformic acid and acrylamide was from 75: 25 to 25: 75, wherein use comprehensive hydrophilic-hydrophobic balance value less than 8 emulsifying surfactant preparation of compositions water-in-oil emulsion, described emulsifying surfactant composition is made up of a kind of pair of block or triblock polymer tensio-active agent and oil soluble radical initiator, and wherein said method also comprises adds a kind of demulsifier surfactant so that promote the anti-phase of emulsion when adding the solution after the polymerization in the entry.
18, method as claimed in claim 17, wherein the mol ratio of vinylformic acid and acrylamide was from 60: 40 to 40: 60.
19, method as claimed in claim 18, wherein said emulsifying surfactant composition is made up of polymeric surfactant and polyoxyethylene-sorbitan mono-oleate, and wherein said polymeric surfactant comprises one or two and derives from the compound monocarboxylic polymer moieties of oil soluble and a water-soluble portion that derives from polyalkylene glycol; The pH value that contains water is 3 to 6; And use 2,2 '-azobis isobutyronitrile is as radical initiator.
20, a kind of composition that comprises cellulose fiber peacekeeping water-soluble anionic copolymers, wherein said multipolymer has following chemical formula:
[-B-co-F-]
Wherein, B is the non-ionic polymers segment that is formed by the unsaturated non-ionic monomer polymerization of one or more vinyl;
F is the anionic polymer chain section that is formed by the unsaturated anionic monomer polymerization of one or more vinyl;
The molar ratio range of B and F was from 95: 5 to 5: 95; And
Described water-soluble anionic copolymers prepares by the water-in-oil emulsion polymerization technique, linking agent of no use;
Wherein said water-in-oil emulsion polymerization technique uses a kind of emulsifying surfactant composition of being made up of two blocks or triblock polymer tensio-active agent and oil soluble radical initiator, and its comprehensive hydrophilic-hydrophobic balance value is less than 8,
Wherein said water-in-oil emulsion polymerization technique comprises the steps:
Prepare the monomeric aqueous solution;
The aqueous solution added in the hydrocarbon liquids contain tensio-active agent or active agent intermixture producing reversed-phase emulsion,
The pH value is adjusted in 2 to 7 the scope,
Make monomer emulsion generation radical polymerization,
When the solution after polymerization adds entry, add extra tensio-active agent and promote the anti-phase of emulsion; And containing the multipolymer Huggins constant that 0.0025 weight % records in the 0.01M NaCl solution of the described multipolymer of 0.025 weight % (k ') greater than 0.75; And contain the described copolymer solution of 1.5 weight % activess in the storage modulus of 4.6Hz (G ') greater than 175Pa.
21, composition as claimed in claim 20, wherein B is selected from acrylamide, Methacrylamide; N-alkyl acrylamide .N, N-dialkyl group-acrylamide; Methyl methacrylate, methyl acrylate; Vinyl cyanide; N-vinyl methylacetamide; N-vinyl methylformamide; Vinylacetate; The N-vinyl pyrrolidone; And the mixture of above-mentioned any compound.
22, composition as claimed in claim 20, wherein F is selected from vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, acrylamide oxyacetic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid, the 2-acrylamide-free acid of 2-methyl-propyl phosphoric acid and the mixture of their salt and above-mentioned any compound.
23, composition as claimed in claim 20, wherein said non-ionic polymers segment B is an acrylamide, described anionic polymer chain section F is selected from acrylic acid sodium salt, sylvite and ammonium salt.
24, prepare the method for polymkeric substance with the water-in-oil emulsion polymerization, comprise following steps:
(a) preparation comprises the oil phase of following composition:
At least a hydrocarbon compound; A kind of surfactant system, comprising at least a pair of block or three block tensio-active agents, it is adding moisture phase time formation emulsion;
(b) preparation comprises the water of following composition:
Unsaturated anionic monomer of at least a vinyl and the unsaturated non-ionic monomer of at least a vinyl;
(c) described water (b) is added formation emulsion and polymerization in the described oil phase (a);
The wherein said pair of block or three block tensio-active agents and monomeric ratio are at least 0.03, and the pH value is adjusted between 2 to 7.
25, method as claimed in claim 24, the comprehensive hydrophilic-hydrophobic balance value of wherein said surfactant system is less than 8.
26, method as claimed in claim 24, wherein the pH value is between 3 to 6.
27, method as claimed in claim 24, the wherein said pair of block or three block tensio-active agents are based on the multipolymer of lipid acid and polyoxyethylated polyester derivatives.
28, method as claimed in claim 24, the unsaturated non-ionic monomer of wherein said vinyl is selected from acrylamide, Methacrylamide; N-alkyl acrylamide, N, N-dialkyl group-acrylamide; Methyl methacrylate, methyl acrylate; Vinyl cyanide; N-vinyl methylacetamide; N-vinyl methylformamide; Vinylacetate; The N-vinyl pyrrolidone; And the mixture of above-mentioned any compound.
29, composition as claimed in claim 24, the unsaturated anionic monomer of therein ethylene base is selected from vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, acrylamide oxyacetic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid, the 2-acrylamide-free acid of 2-methyl-propyl phosphoric acid and the mixture of their salt and above-mentioned any compound.
CNB028243889A 2001-12-07 2002-12-06 Anionic copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions Expired - Lifetime CN1266176C (en)

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ATE456591T1 (en) 2001-12-07 2010-02-15 Hercules Inc ANIONIC COPOLYMERS AVAILABLE IN INVERSE EMULSION AND THEIR USE FOR PRODUCING CELLULOSE FIBER BLENDS
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CN107532076A (en) * 2015-05-13 2018-01-02 艺康美国股份有限公司 Reversible Water-In-Oil latex and application method
CN106279468A (en) * 2015-05-19 2017-01-04 艺康美国股份有限公司 Inverse emulsion polymerization method and for its surface activator composition
CN106279468B (en) * 2015-05-19 2024-06-04 艺康美国股份有限公司 Inverse emulsion polymerization process and surfactant composition therefor

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KR100923611B1 (en) 2009-10-23
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US7250448B2 (en) 2007-07-31
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MX247971B (en) 2007-08-10
PT1451234E (en) 2006-11-30
EP1451234B1 (en) 2006-07-26
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